Background technology
Polytetramethylene ether diol (PTMEG) is a kind of chemical materials, and it is widely used with multi-functional urethanum and polyester and forms segmented copolymer.
As everyone knows, when the preparation polyether glycol, in general, particularly adopt the polymerization of THF (tetrahydrofuran (THF)), and/or in the polymerization of tetrahydrofuran (THF) with comonomer, wherein having used acetate and diacetyl oxide, intermediate product will contain acetoxyl or other end group, before final the use, these groups are transformed into hydroxy functional group with the rear portion.For example; U.S. Patent No. 4,163,115 polymerization and/or the THF that disclose THF generate the polytetramethylene ether diester with the comonomer polymerization; they adopt the fluoride resin catalyzer that contains sulfonic acid group, wherein regulate molecular weight by add acyl group ion parent in reaction medium.This patent disclosure utilize the combination of diacetyl oxide and acetic acid and solid acid catalyst.Be used for recirculation by the unreacted THF of flush away and acetic acid/acetic anhydride and come the separation of polymeric product.Isolating product is the diacetate esters (PTMEA) of polymeric tetrahydrofuran (THF), and it must be transformed into corresponding dihydroxyl product, and polytetramethylene ether diol (PTMEG) is so that be used for most of urethanum end-uses as raw material.Then, the end capped polytetramethylene ether of ester obtains final product polytetramethylene ether diol and byproduct methyl acetate with basic catalyst and alkanol such as methyl alcohol reaction.
United States Patent (USP) 4,230,892 and 4,584,414 disclose the method that PTMEA is transformed into PTMEG, and this method comprises that catalyzer is respectively alkaline earth metal oxide, oxyhydroxide with the alkanol and the catalyst mix of polytetramethylene ether diester with 1-4 carbon atom, perhaps alkoxide and alkali metal hydroxide, or alkali metal alcoholates; Mixture heating up is arrived boiling point, and keep boiling state, the steam of the azeotrope of alkanol and alkyl ester formation simultaneously constantly is removed from conversion zone, finishes substantially up to changing, and removes catalyzer then.At 50 ℃, adopt CaO, in 4 grades of continuous stirred reactors, carry out methanolysis, the result shows, changes not exclusively.In addition, need high-load catalyzer; Methyl alcohol in the vaporization fourth-order reaction device need the input heat, so in the reaction process, energy efficiency is bad.Because above-mentioned a variety of causes, final product PTMEG contains a small amount of unreacted PTMEA, and in urethane reaction, this is undesirable composition.
Disclosure of the present invention
In view of the method that in the past PTMEA was transformed into PTMEG has variety of issue, the invention provides an improved method, can reach transformation fully; And be recovered to and do not contain the unreacted/PTMEA that do not change and the PTMEG of chain triacontanol ester by product.Therefore, the invention provides the method that the polyether glycol diester is changed into corresponding polyether diols polyvalent alcohol, may further comprise the steps:
(a) pack into toward the top of the distillation column following catalyzer of at least a polyether glycol diester and at least a significant quantity: the oxide compound of basic metal or alkaline-earth metal, oxyhydroxide, perhaps alkoxide catalysis, and the C that packs into simultaneously
1-C
4Alkanol makes the polyether glycol diester be transformed into the polyether diols polyvalent alcohol;
(b) feed hot alkanol steam toward the distillation column bottom, the alkanol that purges the polyether glycol diester to the distillation column top decomposes formed chain triacontanol ester;
(c) reclaim distillation capital distilled alkanol and alkanol and decompose formed chain triacontanol ester; With
(d) do not contain the polyether diols polyvalent alcohol that alkanol decomposes formed chain triacontanol ester from the recovery of distillation column bottom.
In one embodiment of the invention, distillation column top overhead product is further separated, and reclaims unreacted alkanol in chain triacontanol ester; The alkanol that obtains in separation is recycled in the distillation column.The polyether glycol diester is the polytetramethylene ether diacetic acid esters preferably in the embodiment at one of the present invention, PTMEA, and catalyzer is a sodium methylate, alkanol is a methyl alcohol, like this, recovery be polytetramethylene ether diol, PTMEG does not contain ritalin.In this better embodiment of the present invention, the reaction distillation column top overhead product that is comprising methyl alcohol and methyl acetate by-product, further carry out the azeotropic separation of methyl acetate, to contain methyl acetate subsequently and be less than 500ppm, and the methyl alcohol that most preferably is less than 100ppm is recycled in the distillation column.
One of target of the present invention provides an improved method, polyether polyol esters is carried out alkanol decompose the generation polyether glycol, adopts the method for reaction distillation, can make like this to react completely.Further object of the present invention is in reactive distillation column, carries out complete separating by-products chain triacontanol ester in polyether glycol simultaneously, so obtain high purity product.Another target of the present invention provides the continuous separation method that distillates logistics from the top of reactive distillation column, so that the recirculation of alkanol to be provided.Read specification sheets of the present invention, and comprised claims and accompanying drawing, and will obviously find out, these targets can reach, and some other target also exists and can reach.
Implement pattern of the present invention
Adopt the solid acid resin catalyst, as molecular weight regulator, as United States Patent (USP) U.S.4, as described in 163,115, tetrahydrofuran (THF) (THF) can polymerization with acetic acid/acetic anhydride.Representative is that under 40-50 ℃ of temperature, THF has 20-40% to be transformed into polymer.Polymerisate is preferably by removing unreacted THF, and removes acetic acid/acetic anhydride the method for its recirculation is separated.The product of separating like this is a polymeric tetrahydrofuran (THF) diacetate esters (PTMEA), and PTMEA must be converted into dihydroxyl product polytetramethylene ether diol (PTMEG) again, so that be used for the end-use of most of urethanum as raw material.
Polyether glycol diester compositions of the present invention, general is any polyethers, for example usually under carboxylic acid and carboxylic acid anhydride existence condition, by the polyethers that a kind of cyclic ethers or mixture produce by the acid catalysis ring-opening polymerization, tetrahydrofuran (THF) is main and/or prevailing reactant in above-mentioned cyclic ethers or the mixture; Promptly be that THF is incorporated in the PTMEA product basically.More particularly, this polyethers diester is by tetrahydrofuran (THF), under the situation of the tetrahydrofuran (THF) comonomer that exists or do not exist alkyl to replace (preferred 3-methyl tetrafluoro furans (3-Me THF) for example), be polymerized, and by tetrafluoro furans (also being to have or do not exist 3-Me THF), also have alkylene oxide, copolymerization obtains during as oxyethane or propylene oxide or suitable comonomer.As mentioned above, the specification sheets of back and the example overwhelming majority are at THF, should be appreciated that simultaneously, can randomly have other comonomers.
In general, the product of starting polymerization process is acetic ester form (or with similar terminal ester group), and under transesterification/alkanol cleavage reaction catalyst existence condition, these products are transformed into the terminal glycol of hydroxyl that is with the methyl alcohol reaction.This reaction requires to use a kind of catalyzer, to obtain rational speed of reaction.The carbinol resolving catalyst of common usefulness comprises sodium methylate (NaOMe), sodium hydroxide (NaOH) and calcium oxide among the present invention.Say that in principle any one high alkalinity alkanol decomposition catalyst all can be used for the purpose of reaction distillation, as United States Patent (USP) 4,230,892 and 4,584, the oxide compound of 414 basic metal of listing or alkaline-earth metal, oxyhydroxide or alkoxide catalysis and their mixture.Useful especially is such some alcoholysis catalysts, and itself has intrinsic and removes outlet capacity, and does not lose activity of such catalysts (for example NaOH/NaOMe/Na2O system, wherein minor amount of water is transformed into the NaOH of catalytic activity).When utilizing NaOH/NaOMe, even at room temperature, speed of response also is fast, so methanol decomposition reaction is under atmospheric pressure carried out.The by product that carries out methanolysis like this is a methyl acetate, and it and methyl alcohol form the lower boiling azeotrope.The alkanol decomposition reaction is a reversible, and therefore, in order to guarantee to reach 100% conversion, it is very important removing evaporable methyl acetate/methanol azeotrope continuously.In the present invention, in reactive distillation column, realize this target, wherein, methanol steam led to tower at the bottom of, purge the methyl acetate in the polymkeric substance.Removed methyl acetate by this method, made transformation efficiency in tower greater than 99.99%.Comparatively speaking, change, need 5 grades of continuous stirred reactors at least in order to reach so completely.
Among the present invention, in single reactive distillation column (RXDC), adopt the adverse current method, realize the fully transformation of PTMEA to PTMEG.More particularly, in the alkanol decomposition reaction, adopting methyl alcohol as alcohol reactant, operate RXDC (reactive distillation column) under 65-70 ℃ and 0-5psig pressure, is to make PTMEA can be transformed into the method for saving cost and effective use of energy sources most of high-quality PTMEG fully.And tradition adopts serial continuous-stirring reactor (CSTR
1S) infusion of financial resources is wanted big several times, consumes the methyl alcohol of several times of amounts more, and the PTMEA that just can reach above-mentioned same degree changes the transformation of PTMEG.
With reference to the accompanying drawings, can explain and understand reaction distillation of the present invention well and how to operate, with the difference of previous method where.Show that as shown in the figure single distillation column 10 is preferred for operate continuously.This reaction distillation, any distillating method and the equipment with operation that can adopt those skilled in the art to understand carry out.Give an example, but be not restriction, the perforated plate column of depth seals on probation.But, the people is felt, traditional perforated plate column should have equal effect.As shown in the figure, the method of using in the preferred example below is, to be substantially free of the polyether polyol esters (in this specific embodiment, being designated as PTMEA on the figure) of unpolymerized THF and acetic anhydride/acetic acid (ACAN/HOAc), be added to the top of distillation tower 10 or near its top.Carbinol resolving catalyst (being that sodium methylate is dissolved in the solution in the methyl alcohol in the present embodiment) also is added in the tower 10, perhaps before adding tower, mix with polyether polyol esters (PTMEA), perhaps be added to polyether polyol esters interpolation point near, the methyl alcohol (hot methanol) of vaporization is added by the bottom near post, so that it with the unreacted PTMEA contact that contains minimum free acetic acid, promotes balance and moves towards the direction that transforms fully under NaOMe/NaOH catalyzer existence condition.The top overhead product of RXDC is the mixture of methyl alcohol with methyl acetate.These top overhead products can be transported in the azeotropic distillation tower, reclaim methyl alcohol (not marking on the figure) under the azeotropic condition.PTMEG and MeOH are drawn out of from RXDC tower 10 bottoms.Superfluous methyl alcohol may be removed in the methyl alcohol elutriator.Under reduced pressure, i.e. 100-450mmHg, elution under 125-145 ℃ of temperature.The PTMEG stream that the result obtains is substantially free of methyl alcohol, contains unreacted transesterification catalyst, NaOMe.Preferably according to United States Patent (USP) 5,410,093 method of describing is removed NaOH.
According to the illustrating of top specific embodiments, what be worth appreciating is, with regard to the object of the invention, crux and very necessary feature are the employing reactive distillation columns, and it relates to elution effect (for rectifying).In other words, in distillation tower bottom or the hot alkanol steam reaction thing of introducing near the bottom to the successive reactivity elution of the chain triacontanol ester that rises and in the reaction of alkanol decompositions/transesterification, form, for making polyether glycol change corresponding polyether diols polyvalent alcohol into, be a brilliant idea with desired total conversion rate.For all practical purposes, the recovery of the distillment of purifying, thus the notion of backflow and/or rectifying can advantageously be finished (for example, under acetate formic acid formation situation, the application that separates azeotropic distillation proves) in knockout tower.Certainly, this does not also mean that, distills and reclaims the sublimed top overhead product that distills and can not carry out in single tower.But say and the invention provides a kind of chance, make and the reaction elution can be separated with recovery and the unreacted alcohol of recirculation.In fact, this also provides a kind of possibility, uses non-distillating method, reaches to separate and recovery top overhead product composition.
Mathematical model points out, in order to reach 99.999% transformation efficiency in RXDC, the concentration of leading to the methyl acetate in the hot methanol stream of RXDC bottom should be less than 100ppm.Methyl acetate concentration in azeotropic tower (not marking among the figure) the bottom methyl alcohol stream is controlled at is lower than the 500ppm level, and most preferably be lower than 100ppm, this can reach.The service temperature of azeotropic distillation tower bottom should be greater than 66 ℃, with the concentration that guarantees methyl acetate less than 100ppm.When methyl acetate concentration was higher, changing to PTMEG for PTMEA in the reactive distillation column can the opposite influence of generation.
Alkanol decomposition method of the present invention is practical, and the result makes PTMEA can fully change PTMEG into.For continuous RXDC process, the amount that needs catalyzer approximately is the 200-1000ppm of PTMEA, and 500-700ppm preferably.If adopt batch formula process, add the catalyzer of analog quantity, then can not get identical productive rate.
(azeotropic of top overhead product reclaims and from the elution of PTMEG product with the operate continuously of methyl alcohol recirculation, the two is all within calculating) during, the amount that needs additional methyl alcohol is to equal to quantize to learn result calculated by the PTMEA in the additive reaction distillation tower (that is to form 1 mole PTMEG basically, need to consume 2 mole, of methanol) add the amount of corresponding consumption in distillation (85%) methyl acetate azeotrope process, produce the recirculation methyl alcohol (i.e. the amount of free methyl alcohol in the byproduct azeotrope) of part this moment.The commercially available methyl alcohol that is used for adding to reactive distillation column generally contains the water that is less than 500ppm, and preferred water content is less than 200ppm.Few like this moisture content is harmless to technological process.In fact, less water makes sodium methylate be transformed into sodium hydroxide.It is and the same effectively catalyzer of sodium methylate.Use sodium methylate and make catalyzer its superiority is obviously arranged, because it can consume minor amount of water, and loss of catalytic activity not.But it is extremely harmful having large quantity of moisture in the system because water lentamente hydrolysis PTMEA produce PTMEG and free acetic acid.The acetate of the Chan Shenging catalyzer that neutralized impels number turnover<50% like this.
In general, in the PTMEA that adds, contain the 50-120ppm free acetic acid methanolysis is not had adverse influence.Acetic acid concentration is higher in reinforced, and the requirement of catalyzer is just bigger, because free acetate reacts with sodium formiate, produces the sodium acetate that does not have catalytic activity.
The existence of unpolymerized THF among the PTMEA does not have substantial influence to the operation and the quality product of process.In the overhead product of the top of reactive distillation column, free THF has just eliminated.In the operate continuously process of this method, do not demonstrate the accumulation phenomena of THF.
Embodiment
In order to show the operation of successive reaction still-process of the present invention, as shown in the figure, making and operate a marked capacity per hour is the single-stage RXDC unit of 100 pounds of PTMEG diacetic acid esterss (representing with PTMEA).This unitary design shows combining of reactive distillation column and azeotropic tower unit operation, to separate and recirculation methyl alcohol.Under 75 ℃, mixture that will contain 99.8% methyl alcohol and 0.2% sodium methylate and the top that is added to the reactive distillation column of depth seals after PTMEA mixed in 3: 1 by volume, simultaneously under 83 ℃, logical methanol steam at the bottom of tower.Overhead product wherein contains 79.6% methyl alcohol and 20.4% methyl acetate 40 ℃ of condensations.Delivered in the azeotropic tower with methyl alcohol by steam stripped methyl acetate.The unreacted methanol sodium (calculating) that contains product P TMEG, 26.2% methyl alcohol and 700ppm at the bottom of the post by wherein not containing methyl alcohol.To the number turnover of PTMEG greater than 99.99% weight.